Amorphous carbon (a-C) films grow via energetic processes such as pulsed-laser deposition (PLD). The cold-cathode electron emission properties of a-C are promising for flat-panel display and vacuum microelectronics technologies. These ultrahard films consist of a mixture of 3-fold and 4-fold coordinated carbon atoms, resulting in an amorphous material with 'diamond-like' properties. We study the structures of a-C films grown at room temperature as a function of PLD energetics using x-ray reflectivity, Raman spectroscopy, high- resolution transmission electron microscopy, and Rutherford backscattering spectrometry. While an understanding of the electron emission mechanism in a-C films remains elusive, the onset of emission is typically preceded by 'conditioning' where the material is stressed by an applied electric field. To simulate conditioning assess its effect, we use the spatially-localized field and current of a scanning tunneling microscope tip. Scanning force microscopy shows that conditioning alters surface morphology and electronic structure. Spatially-resolved electron energy loss spectroscopy indicates that the predominant bonding configuration changes from predominantly 4-fold to 3-fold coordination.